Fungicides



United States Patent 3,173,833 FUNGKJEDES Paul-Ernst Frohberger, Burscheid, Bezirk Dusseldorf, and

Ewald Urbschat, Cologne-Mulheim, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Oct. 24, 1961, Ser. No. 147,169 Claims priority, applicatgizn (ggrmany, Oct. 28, 1960,

8 Claims. in. 167-22) (I) C H:

p-Dimethylamino phenylhydraziue-sulphonate NH N=NS O Me pAmin o-benzene-azo-sulphonate (III) N 132- NHNHS 03MB p-Amino-phenylhydraziuesulph onate p-Aeetylamino-azobenzeuesulphonate (Mezhydrogen or salt forming radicals) Ethylarsine sulfide (EAS) and, more particularly, methylarsine sulfide (MAS) are known to be extraordinarily efficient fungicides. When employed as dressing agent on cereals, MAS exhibits a wide spectrum of activity and is active against practically all the significant species of fungus whose organs of propagation adhere externally to the seed. This universal fungicidal potential, which is similar to that of organic Hg compounds, is not suilicient- 1y expressed when MAS is employed as a dressing agent for seed or as an agent for soil treatment against soil fungi. In the latter case, its activity is limited to the fungi of the Rhizoctonia, Sclerotium, and Thielaviopsis species, the first of which is the more significant economically. Of the same economic importance, however, are other species of fungi such as, e.g. Pythium and Fusarium, which in the form of soil fungi cannot be controlled by MAS.

Since it is impossible to foresee the species of fungi which may develop in various cultivated plants on different soils under a variety of Weather conditions, and which can cause diseases among seedlings and roots, the success of a control of fungis infection originating from the soil is doubtful by means of MAS.

It has now been found that this unreliability of MAS, when employed against soil fungi, can be overcome by combining it with other known fungicides. such as TMTD, DAS, derivatives of DAS, QOBH, and organomercuric 3,173,833 Patented Mar. 16, 1965 compounds. The mixed compositions combine the unsurpassed Rhizoctonia activity of MAS with the wider activity of the second component, and additionally exhibit a degree of activity which exceeds that due to the individual components. Such preparations can be considered for soil treatment as well as for seed treatment. An optimum activity is attained when the individual active agents are contained in it in the proportion of 1:100 to 2:1, the first proportional figure always relating to MAS.

These mixed compositions may, of course, contain inert materials, dressing agents and other plant protecting agents such as fungicides, insecticides, nematicides and agents for the improvement'of soil structure and fertilisers, in addition to the specified agents. They may be formulated in the form of compositions to be scattered, dusted or sprayed, and may constitute granulates, powders, pastes, suspensions, emulsions, and genuine solutions.

The following examples are given for the purpose of illustrating the invention.

Example 1 Greenhouse growth test at temperatures of about 20 C.

Application of the preparations as $011 treatment agents.

Number of healthy Concn. of plants, out of 100 peas, N0. Preparation agent in 3 weeks after sowing soil, as pp as b c d 87 0 2 D 2 10 92 6 89 14 3 25 91 90 4 12 4 100 88 32 64 38 5 MAS DAS 5-1-10 9O 91 88 90 G MAS TMTD 5+95 91 52 90 79 Example 2 Growth tests as in Example 1, except for the difierence that the preparations were employed in the form of seed dressings. The quantity of dressing homogenously applied amounted to 2 g./kg. of seed.

Number of healthy Conan. of plants, out of 100 peas, No. Preparation agent in 3 weeks after sowing dressing, percent a b c d Untreated 87 0 10 0 MAS"--- 10 92 3 78 6 QOBH 5 90 91 14 17 TMTD 93 44 51 MAS Q 7+3 91 93 77 79 MAS TMTD l0+4ll 91 57 68 Example 3 Growth tests in greenhouse at temperatures of about 12 C.

Application of the preparations as seed dressings employed at a rate of 6 g./ kg. of seed.

Number of Conan. of agent healthy plants N Preparation in dressing, out 100 percent clusters,

4 weeks after sowing.

1 Not dressed- 11 MAS 10 115 3 QOBH 30 4- T-M'ID 50 150 PMOl.(phenyl-Hg hl de 3 103 A QQBH 1 7 MAS TMTD 5+45 167 8- MAS-t- PMGL" 5+3 155 e; claim:

A sid l 9mPQ i n @o ain n ts a h thi r m di u de and me r in s lfi e in a at o y Weight of abo t 9 5 2- f iida o0mP$ 9n wnta n W n nam? zoy -hydrazo d met yl a ine vSul d in a ratio y Weight of about 3425-7.

A fu ic da com qsit qn on a n p dim y amino-phenyl diazo-sulfonic acid and methyl alsine sulfide in a ratio by Weight of about 10:5

4. A fungicidal comPQSitiQn, containing sodium p-dimethyl-amino-phenyldiaZo-sulfonate and methyl arsine sulfide in a ratio by weightofabout 10:51?

5. A method for controlling mixed plant fungal infections involving Pytl ium. z ltimumtwith soil fungi sensitive to methyl arsine sulfide, comprisingincorporating into soil v 4 an effective amount of a mixture selected from the group consisting of (a) tetrainethylthiuram,disulfide.with methyl arsine sulfide at a ratio of about 95:5; and (b) p-dimethylamino phenyidiazo-sul'fonate with methyl arsine sulfide at a ratio of about 10:5, the ratios being in parts by Weight. 6. A method for protecting seeds against mixed fungal infection involving Pythium ultimum in combination with additional fungi comprising dressing seeds With a composition containing as active ingredient a mixture selected from the group consisting of (A) tetramethyl-thiuram disulfide with methyl arsine sulfide at a ratio of about 95:5; (B) tetrarnethyl-thiuram disuliide with methyl arsine sulfide at a ratio ot. 40:10; and (C) quinone oximedaenzoyl-hydra- Zone witnmethygl arsine at a ratio-$13 27, the ratios being in parts by'weight. i

7. A fungicidal. composition. containingasactiveingredient a, mixtureseIeCted-frtjmthe group consisting of: (A) tetramethyl thiuram disulfide and methyl arsine sulfide at a ratio ofabout i5 (B) tetramethyl thiurarndisulfide and methyl arsine sulfide at a ratio ofabout 40:10; (C)v q inonex m b nzoyla-Zon n fi by sine sulfide ata ratio of about 3:7; and (D) p-dirnethylamino phenyl diazqsulfonic acid and r methyl arsine sulfide atgara fo 05 about 1 0:5, the ratios being in parts by Weight.

8. A fungicidal composition containing tetrarnethylthiuram disulfide and methyl arsine sulfide in a ratio by weight of, about 40:10.

References Cited in the file of this patent Frear: A Catalogue of Insecticides and Fungicides, vol. II, page 49 (1948).

.Hanna: Handbook of Agricultural Chemicals, 2nd ed.. (1958), pages 193, 199. 

7. A FUNGICIDAL COMPOSITION CONTAINING AS ACTIVE INGREDIENT A MIXTURE SELECTED FROM THE GROUP CONSISTING OF: (A) TETRAMETHYL THIURAM DISULFIDE AND METHYL ARSINE SULFIDE AT A RATIO OF ABOUT 95:5; (B) TETRAMETHYL THIURAM DISULFIDE AND METHYL ARSINE SULFIDE AT A RATIO OF ABOUT 40:10; (C) QUINONE-OXIME-BENZOYL-HYDRAZONE AND METHYL ARSINE SULFIDE AT A RATIO OF ABOUT 3:7; AND (D) P-DIMETHYLAMINO-PHENYL DIAZO-SULFONIC ACID AND METHYL ARSINE SULFIDE AT A RATIO OF ABOUT 10:5, THE RATIOS BEING IN PARTS BY WEIGHT. 